Glass fiber reinforced elastomers

ABSTRACT

A composition for use in the treatment of glass fibers and glass fibers treated with same for use as reinforcement for elastomeric materials in the manufacture of glass fiber reinforced elastomeric products comprising a blend of a resorcinol-aldehyde resin and an elastomer and a coupling system comprising an aminosubstituted organo silicon compound and an organo silicon compound containing at least one beta-haloalkoxy group. The organo silicon compound is formed by the reaction of (a) a halosilane with (b) an alkylene oxide and (c) a monoepoxide or a diepoxide. Alternatively, the organo silicon compound may be prepared by the reaction of (a) a halosilane with (b) a monoepoxide and (c) a diepoxide.

United States Patent [191 McCombs 51 Aug. 19, 1975 GLASS FIBER REINFORCED ELASTOMERS Frank Paul McCombs, Granville,

Ohio

[73] Assignee: Owens-Corning Fiberglas Corporation, Toledo, Ohio [22] Filed: Apr. 27, 1973 [21] Appl. No.: 354,980

[75] Inventor:

[52] US. Cl 428/250; 57/140 C; 260/285 A; 260/28.5 B; 260/293; 260/348 SC; 260/3;

[51] Int. Cl. C07f 7/18; C07d l/00; B32b 17/04 [58] Field of Search ..1 17/126 GS, 126 GN, 117/126 615,126 GB, 72, 76 T;

260/4488 R, 348 SC, 42.15

3.279.886 10/1966 Nitzsche 260/4488 R 3.369.006 2/1968 Brown 260/4488 R 3.555.051 l/.l97l Marsden 260/4488 R 3.787.224 1/1974 Uffner 117/126 GB 5 7] ABSTRACT A composition for use in the treatment of glass fibers and glass fibers treated with same for use as reinforcement for elastomeric materials in the manufacture of glass fiber reinforced elastomeric products comprising a blend of a-resorcinol-aldehyde resin and an elastomer and a icoupling system comprising an aminosubstituted organo silicon compound and an organo silicon compound containing at least one betahaloalkoxy group.

The organo silicon compound is formed by the reaction of (a) a halosilane with (b) an alkylene oxide and (c) a monoepoxide or a diepoxide. Alternatively, the organo silicon compound may be prepared by the reaction of (a) a halosilane with (b) a monoepoxide and (c) a diepoxide.

18 Claims, No Drawings GLASS FIBER REINFORCED ELASTOMERS This invention relates to glass fiber-elastomeric products, and more particularly to the treatment of glass fibers and compositions in the treatment of glass to facilitate the combination of glass fibers with elastomeric materials such as in the manufacture of glass fiberreinforced elastomeric products.

The term glass fibers," as used herein, is intended to refer to and include l continuous fibers formed by rapid attenuation of hundreds of streams of molten glass and to strands formed when such continuous glass fiber filaments are gathered together as they are being formed; and to yarns and cords formed by plying and- /or twisting a number of strands together, and to woven and non-woven fabrics which are formed of such glass fiber strands, yarns or cords, and (2) discontinuous fibers formed by high pressure steam, air or other suitable attenuating force directed onto multiple streams of molten glass issuing from a glass melting bushing or from an orifice containing spinner, ahd to yarns that are formed when such discontinuous fibers are gathered together to form a sliver which is drafted into a yarn; and to woven and nonwoven fabrics formed of such yarns of discontinuous fibers, and (3) combinations of such continuous and discontinuous fibers in strands, yarns, cords and fabrics formed thereof.

As used herein, the term elastomer is intended to mean and include natural rubber in the cured or uncured stage, vulcanized or unvulcanized stage, and syn thetic organic elastomeric materials such as nitriles, acrylics and esters and terpolymers thereof with styrene and acrylonitriles, styrene and vinyl pyridine; and EPDM rubbers as represented by butadiene polymers and copolymers with monoolefins such as butadienestyrene vinyl pyridine terpolymers, chloroprene, isoprene, neoprene, isobutyl rubber and the like elastomeric polymers and copolymers in their cured or un cured stages, and vulcanized or unvulcanized stages. Included also are the EPDM rubbers, such as formed by the interpolymerization of ethylene, an alphamonoolefin having from 32() carbon atoms, such as propylene, and polyene, such as dicyclopentadiene, l ,4-hexadiene and preferably an alkylene or alkylidene norbornene, such as 5-alkylidene-2-norbornene and the like in which the alkylidene group numbers from 2-12 carbon atoms, and polysulfone rubbers.

It is now well known to combine glass fibers with elastomeric materials in the manufacture of glass fiberreinforced elastomeric products, such as driving belts, timing belts, pneumatic tires, etc. One of the problems which has been encountered in such combinations of glass fibers with elastomeric products is the problem of securely anchoring the glass fiber surfaces to the elasto meric material in which the glass fibers are distributed. It is believed that this problem stems in part from the fact that the glass fibers are completely smooth, rodlike members and in part from the fact that the glass fiber surfaces are highly hydrophilic in nature, thereby resulting in the formation of a thin but tenacious film of water on the glass fiber surfaces which serves to destroy any bond. chemical or physical, which would otherwise be formed between the glass fiber surfaces and the elastomeric material with which the glass fibers are combined.

To minimize the problems of bonding the glass fiber surfaces to the elastomeric materials, it has been the practice in the manufacture of glass fiber-reinforced elastomeric products to make use of glass fibers in the form of individual glass fibers having a coating on the surfaces thereof to intertie the individual glass fibers to the elastomeric material in which the glass fibers are distributed, or preferably glass fibers in the form of yarns, cords, chopped strands or fabrics, hereinafter referred to as bundles, containing an impregnant therein which also serves to intertie the glass fiber bundles to the elastomeric material in which the bundles are distributed.

Various compositions may be used in the treatment of glass fibers, either as size compositions for application to the surfaces of individual glass fibers, or as impregnant compositions for impregnation of glass fiber bundles. Conventional size compositions are illustrated in US. Pat. No. 3,424,608 and are generally formed of a film-forming material, a wetting agent and a glass fiber lubricant. Most size compositions now in use are formulated to contain a glass fiber anchoring agent, preferably the form of an organo silane, such as gamma-aminopropyltriethoxy silane or a Werner complex compound.

Impregna'ting compositions now in use are formulated to contain a resorcinol-aldehyde resin component and an elastomer component. Impregnating compositions are illustrated in US. Pat. Nos. 3,424,608 and 3,567,671, as well as numerous others. It has been the practice in the manufacture of glass fiber reinforced elastomeric products to first coat the individual glass fiber filaments with a size composition embodying an organo silicon compound as an anchoring agent, and then impregnate a bundle of the sized fibers with an impregnating composition formulated of a resorcinolaldehyde resin component and an elastomer component. The resulting bundle can then be combined with an elastomeric material in the manufacture of glass fiher-reinforced elastomeric products.

The size coating on the individual glass fibers is believed to improve the processing characteristics of the glass fibers without destroying their fibrous characteristics and to promote the bonding relationship between the elastomeric component of the impregnant. The impregnant is believed to intertie the impregnated bundle with the elastomeric material constituting the continuous phase with which the bundles are combined.

It has been proposed to modify the above described practice by eliminating one step of the sizing and impregnating technique. Such proposals most frequently suggest that the impregnating composition be applied directly to the individual glass fibers, preferably as they are formed, to form a coating thereon. However, it has been found that the bonding relationship between glass fibers treated in this manner and elastomeric materials is poor unless the impregnating composition is formulated to contain an organo silicon compound as an anchoring agent.

Such anchoring agents can be formulated with impregnating compositions of the type described above. However, the resulting composition is not completely stable because the highly acidic nature of the organo silicon compounds tends to cause coagulation of the latex containing the resorcinol-aldehyde resin and the elastomer.

It is therefore an object of the present invention to provide a composition for use in the treatment of glass fibers which contains a resorcinol-aldehyde resin comtex.

The concepts of this invention reside in a composition for use in the treatment of glass fibers in which a latex containing a resorcinol-aldehyde resin and an elastomer is formulated to include an organo silicon compound containing at least one organic group attached directly to the silicon which is substituted with at least one amino group and at least one organo silicon compound containing at least one beta-haloalkoxy group wherein X is halogen.

Without limiting the present invention as to theory, it is believed that the beta-haloalkoxy group referred to above, which is significantly more resistant to hydrolysis in aqueous media as compared to organo silicon compounds containing a simple alkoxy group, stabilizes the amino substituted organo silicon in the alkaline latex composition to prevent or substantially minimize coagulation of the latex and thereby assure stability in the resulting composition. In addition, the organo silicon compounds containing the beta-haloalkoxy group contribute to the improved bonding relationship between the glass fibers and the elastomer component of the impregnant.

The resulting composition can be applied to the individual glass fibers to form a coating on the surfaces thereof, or to a bundle of sized or unsized glass fibers as an impregnant, to improve the bonding relationship between the glass fibers and an elastomeric material with which the treated glass fibers are combined in the manufacture of glass fiber-reinforced elastomeric products.

As the amino-substituted organo silicon compound, use is preferably made of at least one silane containing 1 to 3 readily hydrolyzable groups and containing at least one organic group attached directly to the silicon atom, with at least one of the organic groups being substituted by at least one amino group. Any remaining valences on the silicon atom are taken up by hydrogen. Such silanes are hydrolyzable in aqueous media and, thus, use can also be made of the corresponding hydrolysis products of such silanes, specifically the corresponding silanols and siloxanes.

It is frequently advantageous to first hydrolyze the silane with aqueous media prior to formulating the composition of this invention. Such hydrolysis is preferably effected by simply contacting the silane with water or an aqueous alkaline solution containing an emulsifying agent to facilitate dispersion of the silane.

The silanes most preferred for use in the practice of this invention are themselves well known to the art, and include silanes having the formula wherein R is a divalent organic group containing 2 to 10 carbon atoms, such as alkylene (i.e., dimethylene, trimethylene, tetramethylene, pentamethylene, etc.), alkenylene (i.e., ethenylene, propenylene, etc.), cycloalkylene (i.e., cyclopentylene, cyclohexylene, etc.) or arylene (i.e., phenylene, etc.); R is an organic group and preferably a hydrocarbon group containing 1 to 6 carbon atoms including alkyl (i.e., methyl, ethyl, isopropyl, etc.), alkenyl (i.e., vinyl, allyl, etc.), cycloalkyl containing 4 to 6 carbon atoms (i.e., cyclopentyl, cyclohexyl, etc.) or phenyl, including the hydroxy, epoxy or mercapto derivatives thereof; Z is a readily hydrolyzable group, such as halogen (chlorine or bromine) or a C to C alkoxy group (i.e., methoxy, ethoxy, propoxy, etc.); n is an integer from 1 to 3 and m is O or 1. Also suitable for use in this invention are the hydrolysis products thereof.

Illustrative of such silanes include the following: gamma-aminopropyltrimethoxysilane delta-aminobutyltriethoxysilane p-aminophenyltriethoxysilane 3-aminocyclohexyltrimethoxysilane beta-aminovinyltrimethoxysilane gamma-aminoallyltrimethoxysilane bis-( gamma-aminopropyl )diethoxysilane beta-aminoethylmethyldiethoxysilane gamma-aminopropylallyldiethoxysilane and the corresponding hydrolysis products thereof including the silanols and siloxanes of each of the foregoing silanes.

Also suitable for use in the practice of this invention are polyamino silanes; these silanes have the general formula wherein a is an integer from 1 to 3, b is an integer from I to 3, c is an integer from 1 to 3, d is l to 2, and Z is as described above.

Such silanes include the following: H N-CH CH NHCH CH -CH- 2- a)a (H NCH -CH NHCH CH CH Si- 2 5)2 H N-CH --Cl-l Cl-l NHCl-l -CH- 2 3)3 H NCH --Cl-l NH-CH CH NHCH- CH CH Si(OCI-l and the corresponding hydrolysis products thereof.

Another amino silicon compound which can advantageously be used in the practice of the invention is the polyamino-functional silane marketed by Dow Corning, first under the trademark XZ-2-2287 and now under the trademark Z-6050. The polyamino silane is prepared by reaction of the compounds wherein R is C, to C alkyl (e.g., methyl, ethyl, propyl, etc.) with ethylene imine to form the compounds represented by the following:

wherein R is a divalent organic radical such as oxyalkyleneoxy containing 1 to carbon atoms; oxyalkyleneoxyalkyleneoxy containing 2 to carbon atoms,

, divalent aromatic groups such as a group of the formula The organo silicon compounds containing the betahaloalkoxy groups as described above are described in detail in copending applications Ser. No. 347,264, filed Apr. 2, 1973 and Ser. No. 347,241, filed Apr. 2, 1973 both of which are assigned to the assignee of this invention. As described in the foregoing copending application Ser. No. 347,264, the compounds are prepared by reaction of a halosilane (7) wherein R is an organic group, and preferably alkyl (i.e., methyl, ethyl, propyl, etc.), alkenyl (i.e., vinyl, alv R -CHCH (8) wherein R is C, to C alkyl or hydrogen and either l a monoepoxide in the form of styrene oxide or a monoepoxide of the formula 0 wherein R is an aryl group and preferably phenyl or phenyl substituted with an amino group, a halogen group, an alkyl group; alkyl containing 1 to 20 carbon atoms and substituted derivatives thereof; an alkenyl group containing 2 to 8 carbon atoms (e.g., vinyl, allyl,

etc.); a group having the formula wherein R is hydrogen or methyl; (2) a diepoxide having the formula or (3) a cycloalkane diepoxide including the following compounds:

-cH- H O j v n (RD 4 or ERL 4206) (ERR 4205 i? CH OC(CH ).,'C 0 cl-i (ERR 4289) COCH 0 ll (ERR 422 1 Illustrative of such monoepoxides are phenyl glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, a mixture of n-octyl and n-decyl glycidyl ethers (Epoxide No. 7 from Procter and Gamble) and a mixture of n-dodecyl and n-tetradecyl glycidyl ethers (Epoxide No. 8 from Procter and Gamble). 1

A number of such diepoxides are commercially available for Dow'and Ciba and include the following:

In the preparation of such compounds, use is generally made of l to 3 epoxide equivalents of the alkylene oxide and 0.5 to 3 epoxide equivalents of the monoor diepoxides described above. Where the epoxide em- 25 ployed is a diepoxide, it is generally preferred that the total of e plus the epoxide equivalents of the alkylene oxide total at least 2.1 and preferably at least 2.5 to minimize gel formation.

The resulting reaction product is most frequently a 0 mixture of compounds which is preferably used as such without separation of individual compounds thereof; however, it will be understood that the predominant compounds contained in the reaction mixture can be separated and utilized in the practice of this invention. 35 Specific compounds prepared can be illustrated by way of the following:

wherein f and g are each integers from 1 to 3; or

Where the epoxide is a diepoxide, the reaction product includes compounds containing no free epoxy group and/or compounds containing free epoxy groups;

the reaction can be illustrated by the following: 60

and/or The preparation of compounds containing the free epoxy group is generally favored by employing 2 or more epoxide equivalents of the diepoxides. As will be appreciated by those skilled in the art and as is described in the foregoing copending applications, analogous compounds are prepared where c is l or 2, with 15 the valence of the beta-haloalkoxy groups being decreased correspondingly.

As is also described in the foregoing copending applications, the alkylene oxide can be replaced in whole or in part by a monohydric alcohol.

Organo silicon compounds preferred for use in the practice of this invention are those prepared using propylene oxide and DER 332, using 3 epoxide equivalents of the propylene oxide and l epoxide equivalent of the diepoxide. The product of this reaction is a mixture which contains the compound and (2) at least one of the diepoxides described above, as described in copending application Ser. No. 347,241. In this embodiment of the invention, the reaction product is preferably prepared using 1 to 3 epoxide equivalents of l) and 0.5 to 3 epoxide equivalents of (2). If desired, a portion of the styrene oxide or monoepoxide (1) can be replaced by a monohydric alcohol and/or a lower alkylene oxide in amounts up to 2 moles of alcohol and/or alkylene oxide per mole of the halosilane.

The reaction product is generally in the form of a mixture of compounds, and it is generally preferred that the product be utilized as such. The reaction product contains compounds containing at least 2 betahaloalkoxy groups, and the specific compounds produced can be illustrated by way of the following:

Another preferred reaction product is that prepared 35 using 3 epoxide equivalents of propylene oxide and 1 epoxide equivalent of DER 1359; this reaction product includes the following compound:

with (1) either a styrene oxide or a monoepoxide R ,O-CH CHCH 30 and/or and/or in the above equations can be replaced by R groups, the residue of an alkylene oxide, and/or the residue of the monohydric alcohol.

For further description of the foregoing betahaloalkoxy compounds, reference can be made to the foregoing copending applications, the disclosures of which are incorporated herein by reference.

The relative proportions of the amino-substituted organo silicon compounds and the beta-haloalkoxy compounds are not critical, and can be varied within wide limits. It has been found that best results are usually obtained where the total of the amino-substituted organo silicon compound and the beta-haloalkoxy compound contains 1 to 35 percent, and preferably 5 to 30 percent by weight of the amino-substituted organo silicon compound.

The amount of the silicon compounds employed with the blend of the elastomer and the resorcinol-aldehyde resin components is likewise not critical to the practice of the invention. It is generally sufficient that the total of the siliconcontaining compounds constitute from 0.1 to percent, and preferably 1 to 15 percent of the total solids of the treating composition.

The treating compositions with which the silicon compounds are formulated are generally well-known to those skilled in the art and are described in US. Pat. Nos. 3,391,052; 3,402,064, 3,424,608; 3,506,476; 3,533,830; 3,567,671; 3,591,357 as well as others.

Such compositions are generally formulated to contain 1 to 10 parts by weight of a resorcinol-aldehyde resin component and 20 to parts by weight of at least one elastomer on a solids basis. Some of such compositions are formulated to contain other polymeric components to provide treated glass fibers having the desired degree of stiffness and tackiness; such polymeric additives are fully described in the foregoing patents.

The treating composition formulated in accordance with the practice of the present invention is preferably applied to glass fibers as they are formed to form a thin coating of the solids of the composition along with the silicon compounds. In general, it is preferred that the composition be applied in an amount sufficient to provide a coating constituting l to 20 percent by weight of the glass fibers. Subsequent to coating, the glass fibers can be gathered together in a conventional manner to form strands, which in turn can be twisted and plied together to form cords, without the need of subsequent processing, for combination with elastomeric materials in the manufacture of glass fiber-reinforced elastomeric products.

Alternatively, the treating composition of this invention can be applied as an impregnating composition to bundles of glass fibers, which preferably but not necessarily have a thin film of coating of a glass fiber size on the individual surfaces. Techniques for impregnation are now well known and are described in the foregoing patents; bundles of glass fibers are preferably immersed in a bath of the treating composition of the invention and subjected to a sharp bend while immersed therein to open the bundle and permit complete penetration of the composition into the bundle whereby the solids of the composition serve to separate the fibers each from the other and fill the interstices between the fiber filaments to define a unitary bundle structure. Impregnation is generally carried out to deposit from 5 to 30 percent dry solids in the glass fiber bundle.

Having described the basic concepts of the invention, reference is now made to the following examples which are provided by way of illustration, and not by way of limitation, of the practice of the invention in the formulation of the treating composition of the invention and its use in the treatment of glass fibers.

EXAMPLE 1 Using the procedure described in Example 1 copending application Ser. No. 347,264, 1 mole of silicon tetrachloride is reacted with 0.5 mole 1 epoxide equivalent) of DER 332 and 3 moles of propylene oxide.

A sample of 80 g of the reaction product is then mixed with 50 g of an emulsifying agent RL 3773, which is an amphoteric sulfated oil from Procter Chemical. To the resulting mixture, there is added 20 g of gamma-aminopropyltriethoxy silane (A1 100 from Union Carbide) in 100 g of deionized water. The resulting mixture is then blended with 2,000 g of a glass fiber treating composition of the type described in US. Pat. No. 3,567,671.

The resulting composition contained the following:

Parts by weight Silicon compound mixture (plus emulsifier) 150 Resorcinol-formaldehyde resin (Penacolyte R2120 7571 solids) 48 Vinyl pyridine-butadiene-styrene terpolymer (Gentac FS General Tire and Rubber Co. 42% solids) 900 Vinyl chloride-vinylidene chloride copolymer (Dow latex 874 50% solids) 350 Microcrystalline paraffin wax (Vultex Wax No. 5 5671 solids) 200 Water 602 EXAMPLE 2 Using the procedure described in Example 4 of Ser. No. 347,264, 1 mole of SiCl. is reacted with 3 moles of propylene oxide and 0.5 mole l epoxide equivalent) of the epoxide ERE 1359.

A sample of 83.3 g of the reaction product is mixed with g of an emulsifier (CA 630 from GAF Corp.

which is an octylphenoxypoly(ethyleneoxy)ethanol).

The resulting mixture is then blended with 16.7 g of gamma-aminopropyltriethoxy silane, and this mixture is blended with 2,000 g of the composition employed in Example 1 to form the following composition:

Parts by weight Silicon compound mixture-(plus emulsifier) 1 10 Resorcinol-formaldehydc resin solids) 48 Vinyl pyridine-butadiene-styrcne tcrpolymcr (42% solids) 900 Vinyl chloridc-vinylidene chloride copolymer (50% solids) 350 Microcrystulline paraffin wax (56% solids) 200 Water A bundle of glass fibers is subjected to impregnation with the final composition using the procedure described in Example 1. The resulting bundle in the form of a cord is subjected to analysis and found to have a loss on ignition (L01) of 19.8 percent and a tensile strength of 72.3 lbs. A sample of the cord is also molded between the strips of rubber to determine the hot U-adhesion value which is found to be 28.9 lbs.

EXAMPLE 3 Using the procedure described in Example 1, the adduct of SiCl propylene oxide and DER 332 is prepared, and the resulting product is subjected to purification by chromatography to isolate the compound A sample of g of the above compound is mixed with 50 g of the emulsifying agent RL 3773 and 20 g of gamma-aminopropyltrimethoxysilane in g of water. The resulting mixture is then blended with a blend of a resorcinol-aldehyde resin and an elastomer to form the following composition:

Parts by weight Silicon compound mixture (plus emulsifier) Resorcinol-formaldehyde resin (75% solids) 50 Vinyl pyridine butadiene-styrene terpolymer (42% solids) I 800 Water 400 The above composition can be applied to individual glass fiber filaments, preferably as they are formed, to form a coating on the surfaces thereof, or as an impregnant.

EXAMPLE 4 A sample of 15 g of the polyamino functional silane Z6050 in isopropanol is first hydrolzed with water and then blended with a mixture of 60 g of the reaction product described in Example 1 above and 40 g of emulsifying agent RL 3773. The resulting mixture is then blended with 2,000 g of a glass fiber treating composition of the type described in US. Pat. No. 3,567,671, except that the vinyl chloride-vinylidene chloride component is replaced by a dicarboxylated butadiene-styrene copolymer component to form the following:

The dicarboxylated butadiene-styrene copolymer is, as indicated, marketed by Goodyear Tire and Rubber Co. and has been found to be markedly superior to the monoearboxylated copolymer described in the foregoing US. Pat, No. 3,567,671. Other dicarboxylated butadiene-styrene eopolymers which can be used in lieu of the Pliolite 4121 include Pliolite 4264, Pliolite 4303, Pliolite 386, Pliolite 402 and Pliolite 388. These copolymers have a ratio of styrene to butadiene of at least 50/50, and generally within the range of 50/50 to 85/15, and are prepared by polymerization of butadiene and styrene in the presence of small amounts of a dicarboxylic acid containing ethylenic unsaturation, with less than 2 percent emulsifier.

EXAMPLE 5 Using the procedure described in Example 4, 20 g of the polyamino functional silane Z-6050 hydrolyzed.

with water is admixed with 80 g of the SiCh-epoxide reaction product described in Example 2 and 50 g of emulsifying agent RL 3773.

The resulting mixture is then combined with 2,200 g of the treating composition described in Example 4 to form the following composition:

Water General examples of the foregoing glass fiber treating compositions may be illustrated by way of the following example in which all but the mixture of the aminosubstituted organo silicon compound and the betahaloalkoxy silicon compounds are expressed on a solids basis:

EXAMPLE 6 Parts by weight solids Silicon compound mixture 4 35 Resorcinolaldehyde resin 2 10 Vinyl pyridine-butadiene-styrene terpolymer 20 60 Vinyl chloride-vinylidene chloride copolymer or d carboxylated butadiene styrene copolymer l5 40 Microcrystalline paraffin wax EXAMPLE 7 Using the procedure described in Example -2, the SiCl -epoxide described therein is prepared and subjected to purification to separate as the major constituexit the following compound:

This compound is then admixed with delta-aminobutyltrimethoxysilane which has been hydrolyzed with water. The resulting mixture is then formulated with a composition of the type described above in Example 5 as follows:

Parts by weight solids Silicon compound mixture 6 Resorcinol-formaldehyde resin 5 Vinyl pyridine-butadiene-styrene terpolymer 35 Dicarboxylated butadiene-styrene copolymer 25 Microcrystalline paraffin wax 5 EXAMPLE 8 Twenty grams of N-(beta-aminoethyl)gammaaminopropyltrimethoxy silane is hydrolyzed with water and blended with g of the adduct formed by reaction of SiCl propylene oxide and glycidyl methacrylate in a mole ratio of 1:3:[ as described in Example 7 of copending application Ser. No. 347,264 to which 10 g of emulsifying agent (Emulsifier 221 from Sylvan Chemicals, which is an aryl polyoxyether) has been added.

The resulting silicon compound mixture is then blended with an RFL system to form the following impregnating composition:

Parts by weight solids Silicon compound mixture (plus emulsifier) 3.0 Resorcinol-formaldehyde resin 5.0 Vinyl pyridine-butadiene-styrcne terpolymer 30.0

EXAMPLE 9 Using the procedure described in Example 10 of copending application Ser. No. 347,264, the adduct of SiCl propylene oxide and epoxide ERR 4205 is prepared, and 90 g of the reaction product is blended with 20 g of emulsifying agent. The resulting mixture is then blended with 10 g of p-aminophenyltriethoxysilane which had been hydrolyzed with water.

The resulting mixture of silicon compounds is blended with an RFL system to form the following composition:

Parts by weight solids Silicon compound mixture (plus emulsifier) 1.5 Resorcinol-formaldchyde resin 4.0 Natural rubber 25.0

' EXAMPLE l 7 The adduct of 1 mole SiCl 2 moles of propylene oxide and 1 mole of epoxide DER 332 described in Example 18 of Ser. No. 347,264 is mixed with hydrolyzed Z-6050. The resulting mixture of silicon compounds is formulated into the following composition of the type described in U.S. Pat. No. 3,424,608:

Parts by weight solids Silicon compounds mixture (plus emulsifier) 4 30 ResorcinoLformaldehyde resin 2 Vinyl pyridine-butadienc-styrene terpolymer l5 50 Neoprene rubber 25 50 Polybutadiene 5 In a like manner, the compositions described in Examples 19 to 34 of copending application Ser. No. 347,264 can be employed in treating compositions of the type described in Examples 1 to 10 in lieu of the complex haloalkoxy compounds disclosed. Similarly, use can also be made of the beta-haloalkoxy groups described in copending application Ser. No. 347,241 as represented by the following examples.

EXAMPLE 1 1 Parts by weight Silicon compound mixture 150 Resorcinol-formaldehyde resin (Penacolyte R2120 7571 solids) 48 Vinyl pyridine-butadicne styrenc terpolymer (Gentac FS General Tire and Rubber Co. 42% solids) 9(X) Vinyl chloridcvinylidcne chloride copolymer (Dow latex 874 50% solids) 350 Microcrystullinc paraffin wax (Vultcx Wax No 5 4 56% solids) 200 Writer 602 EXAMPLE 12 The raw reaction mixture described in Example 5 of copending application Ser. No. 347,241 is blended with an emulsifier and 15 grams of the polyamino functional silane Z-6050. The resulting composition is then blended with an impregnating composition of the type described above in Example 4, forming the following composition.

In like manner, each of the products of Examples 6' through 37 of copending application Ser. No. 347,241 can be employed in lieu of the beta-haloalkoxy silicon compounds exemplified in these two Examples.

As indicated, the compositions of Examples l-l 2 can be employed in the treatment of individual glass fibers, forming a thin coating thereon, or the compositions can be applied as an impregnant to bundles of glass fibers which preferably have been previously sized with a glass fiber size composition. The resulting treated glass fibers or bundlesof glass fibers can thereafter be combined directly with plastic resins in the manufacture of glass fiber reinforced plastics, laminates, coated fabrics and the like. It is generally preferred that the coated fibers be combined with plastic resins as described whereby the coating on the surfaces of the individual glass fiber filaments operates to securely anchor the glass fibers to the plastic resin. As used herein, the term plastic resin refers to and includes thermoplastic and thermosetting resins, such as polyesters, polyepoxides, polyamides, etc.

In the preferred use, glass fibers or bundles of glass fibers which have been treated in accordance with the present invention are employed as reinforcement for elastomeric materials in the manufacture of glass fiberreinforced elastomeric products, such as rubber tires, drive belts, V-belts, etc. Regardless of whether bundles or individually coated glass fibers are employed, the composition of this invention serves to intertie the glass fibers with the elastomeric material to securely bond the glass fibers thereto.

In facilitating the combination of glass fibers treated in accordance with the present invention with elastomeric materials, the individually coated fibers or the impregnated bundles of glass fibers are mixed with an elastomeric material or otherwise laid down in the desired arrangement for combination with the elastomeric material as in the manufacture of glass fiberreinforced elastomeric products. The resulting combination of glass fibers and elastomeric material is processed in a conventional manner by molding or curing under heat and compression for advancement of the elastomeric material to a cured or vulcanized stage while in combination with the treated glass fibers or bundles of glass fibers whereby the glass fibers or bundles of glass fibers become strongly integrated with the elastomeric material in the glass fiberreinforced elastomeric product.

In the final system, the elastomeric material with which the glass fibers or bundles of glass fibers are combined, constitutes a continuous phase. Such continuous phase elastomeric materials may comprise elastomers or rubbers of the type incorporated into the treating compositions or the elastomeric material can differ therefrom. It is believed that the tie-in between the individually coated glass fibers or the impregnated bundles of glass fibers and the elastomeric materials forming the continuous phase occurs primarily during cure or vulcanization of the elastomeric material in combination with the treated glass fibers.

It will be apparent that various changes and modifications can be made in the details of procedure, formulation and use without departing from the spirit of the invention, especially as defined in the following claims.

I claim:

1. Glass fibers having a coating thereon, said coating comprising (A) a blend of resorcinol-aldehyde resin and an elastomer and (B) from 0.1 to 25 percent by weight of a combination of organo silicon compounds comprising 1 to 35% of (1) an amino-substituted organo silane or its hydrolysis products and 99 to 65% of (2) an organo silicon compound containing at least one beta-haloalkoxy group in the form of a reaction product of (a) a halosilane ah M-e) wherein R is an organic group, X is halogen and e is O or an integer from 1 to 2, (b) an alkylene oxide containing 2 to 6 carbon atoms aand (c) an epoxide selected from the group consisting of a monoepoxide of the formula wherein R is a functional organic group selected from the group consisting of aryl, alkyl and substituted alkyl, alkenyl and acryl group and a methacryl group; a diepoxide of the formula wherein R is a divalent organic group selected from the group consisting of oxyalkyleneoxy, oxyalkyleneoxyalkyleneoxy and a divalent aromatic group; and a cycloalkane diepoxide, with the reaction product containing l to 3 epoxide equivalents of (b) and 0.5 to 3.0 epoxide equivalents of (e) per mole of halosilane.

2. Glass fibers as defined in claim 1 wherein the halosilane is a silicon tetrahalide.

3. Glass fibers as defined in claim 1 wherein (c) is selected from the group consisting of a compound of the formula CH O and a compound of the formula 4. Glass fibers as defined in claim 1 wherein the coating also contains a material selected from the group consisting of a vinyl chloride-vinylidene chloride copolymer, a microcrystalline paraffin wax, a carboxylated butadienestyrene copolymer and mixtures thereof.

5. Glass fibers as defined in claim 4 wherein the carboxylated copolymer is a dicarboxylated copolymer.

6. Glass fibers as defined in claim 1 wherein the coating contains 2 to 10 parts by weight of the resorcinolaldehyde resin per 20 to 100 parts by weight of the elastomer.

7. Glass fibers as defined in claim 1 wherein the coating is a coating on the individual glass fiber filaments.

8. Glass fibers as defined in claim 1 wherein the glass fibers are in the form of a bundle, and the coating constitutes an impregnant in the bundle.

9. Glass fibers as defined in claim 8 wherein the individual fibers forming the bundle have a thin size coating on the surfaces thereof.

10. Glass fibers as defined in claim 8 wherein the bundle is formed of a plurality of strands which have been plied and twisted together to form a cord.

11. Glass fibers as defined in claim 8 wherein the bundle is formed of a woven or non-woven fabric.

12. In a glass fiber-reinforced elastomeric product wherein an elastomeric material constitutes a continuous phase in which the glass fibers are distributed, the improvement in the bonding relationship between the glass fibers and the elastomeric material comprising glass fibers as defined in claim 1.

13. Glass fibers having a coating thereon, said coating comprising (a) a blend of 2 to 10 parts by weight of a resorcinol-aldehyde resin, 20 to parts by weight of a vinyl pyridine-butadiene-styrene terpolymer, 15 to 40 parts by weight of a polymeric material selected from the group consisting of a vinyl chloride-vinylidene chloride copolymer and a carboxylated butadienestyrene copolymer and 3 to 30 parts by weight of a microcrystalline paraffin wax, and (b) from 0.1 to 25 percent by weight of a combination of organo silicon compounds comprising (1) l to 35 percent by weight of an amino-substituted organo silane or its hydrolysis product and (2) 99 to percent by weight of an organo silicon compound containing at least one beta-haloalkoxy group in the form of the reaction product of (a) a halosilane (R SiX wherein R is an organic group, X is halogen and e is O or an integer from 1 to 2, (b) an alkylene oxide containing 2 to 6 carbon atoms and (c) an epoxide selected from the group consisting of a monoepoxide of the formula wherein R is a functional organic group selected from the group consisting of aryl, alkyl and substituted alkyl, alkenyl and acryl group and a methacryl group; a diepoxide of the formula 16. Glass fibers as defined in claim wherein R is selected from the group consisting of a group of the formula and a group of the formula 17. Glass fibers as defined in claim 13 wherein the carboxylated copolymer is a dicarboxylated butadienestyrene copolymer.

18. In a glass fiber-reinforced elastomeric product wherein an elastomeric material constitutes a continuous phase in which the glass fibers are distributed, the improvement in the bonding relationship between the glass fibers and the elastomeric material comprising glass fibers as defined in claim 13. 

1. GLASS FIBERS HAVING A COATING THEREON, SAID COATING COMPRISING (A) A BLEND OF RESORCINOL-ALDEHYDE RESIN AND AN ELASTOMER AND (B) FROM 0.1 TO 25 PERCENT BY WEIGHT OF A COMBINATION OF ORGANO SILICON COMPOUNDS COMPRISING 1 TO 35% OF (1) AN AMINO-SUBSTITUTED ORGANO SILANE OR ITS HYDROLYSIS PRODUCTS AND 99 TO 65% OF (2) AN ORGANO SILICON COMPOUND CONTAINING AT LEAST ONE BETA-HALOALKOXY GROUP IN THE FORM OF A REACTION PRODUCT OF (A) A HALOSILANE
 2. Glass fibers as defined in cLaim 1 wherein the halosilane is a silicon tetrahalide.
 3. Glass fibers as defined in claim 1 wherein (c) is selected from the group consisting of a compound of the formula
 4. Glass fibers as defined in claim 1 wherein the coating also contains a material selected from the group consisting of a vinyl chloride-vinylidene chloride copolymer, a microcrystalline paraffin wax, a carboxylated butadienestyrene copolymer and mixtures thereof.
 5. Glass fibers as defined in claim 4 wherein the carboxylated copolymer is a dicarboxylated copolymer.
 6. Glass fibers as defined in claim 1 wherein the coating contains 2 to 10 parts by weight of the resorcinolaldehyde resin per 20 to 100 parts by weight of the elastomer.
 7. Glass fibers as defined in claim 1 wherein the coating is a coating on the individual glass fiber filaments.
 8. Glass fibers as defined in claim 1 wherein the glass fibers are in the form of a bundle, and the coating constitutes an impregnant in the bundle.
 9. Glass fibers as defined in claim 8 wherein the individual fibers forming the bundle have a thin size coating on the surfaces thereof.
 10. Glass fibers as defined in claim 8 wherein the bundle is formed of a plurality of strands which have been plied and twisted together to form a cord.
 11. Glass fibers as defined in claim 8 wherein the bundle is formed of a woven or non-woven fabric.
 12. In a glass fiber-reinforced elastomeric product wherein an elastomeric material constitutes a continuous phase in which the glass fibers are distributed, the improvement in the bonding relationship between the glass fibers and the elastomeric material comprising glass fibers as defined in claim
 1. 13. Glass fibers having a coating thereon, said coating comprising (a) a blend of 2 to 10 parts by weight of a resorcinol-aldehyde resin, 20 to 60 parts by weight of a vinyl pyridine-butadiene-styrene terpolymer, 15 to 40 parts by weight of a polymeric material selected from the group consisting of a vinyl chloride-vinylidene chloride copolymer and a carboxylated butadiene-styrene copolymer and 3 to 30 parts by weight of a microcrystalline paraffin wax, and (b) from 0.1 to 25 percent by weight of a combination of organo silicon compounds comprising (1) 1 to 35 percent by weight of an amino-substituted organo silane or its hydrolysis product and (2) 99 to 65 percent by weight of an organo silicon compound containing at least one beta-haloalkoxy group in the form of the reaction product of (a) a halosilane (R3)e SiX(4-e) wherein R3 is an organic group, X is halogen and e is 0 or an integer from 1 to 2, (b) an alkylene oxide containing 2 to 6 carbon atoms and (c) an epoxide selected from the group consisting of a monoepoxide of the formula
 14. Glass fibers as defined in claim 13 wherein the halosilane is a tetrahalosilane.
 15. Glass fibers as defined in claim 13 wherein (c) is a diepoxide of the formula
 16. Glass fibers as defined in claim 15 wherein R6 is selected from the group consisting of a group of the formula
 17. Glass fibers as defined in claim 13 wherein the carboxylated copolymer is a dicarboxylated butadienestyrene copolymer.
 18. In a glass fiber-reinforced elastomeric product wherein an elastomeric material constitutes a continuous phase in which the glass fibers are distributed, the improvement in the bonding relationship between the glass fibers and the elastomeric material comprising glass fibers as defined in claim
 13. 